Thermal Activation of CH4 and H2 as Mediated by the Ruthenium Oxide Cluster Ions [RuOx]+ (x=1–3): On the Influence of Oxidation States

Thermal gas-phase reactions of the ruthenium-oxide clusters [RuO_x]⁺ (x=1–3) with methane and dihydrogen have been explored by using FT-ICR mass spectrometry complemented by high-level quantum chemical calculations. For methane activation, as compared to the previously studied [RuO]⁺/CH₄ couple, the higher oxidized Ru systems give rise to completely different product distributions. [RuO₂]⁺ brings about the generations of [Ru,O,C,H₂]⁺/H₂O, [Ru,O,C]⁺/H₂/H₂O, and [Ru,O,H₂]⁺/CH₂O, whereas [RuO₃]⁺ exhibits a higher selectivity and efficiency in producing formaldehyde and syngas (CO+H₂). Regarding the reactions with H₂, as compared to CH₄, both [RuO]⁺ and [RuO₂]⁺ react similarly inefficiently with oxygen-atom transfer being the main reaction channel; in contrast, [RuO₃]⁺ is inert toward dihydrogen. Theoretical analysis reveals that the reduction of the metal center drives the overall oxidation of methane, whereas the back-bonding orbital interactions between the cluster ions and dihydrogen control the H−H bond activation. Furthermore, the reactivity patterns of [RuO_x]⁺ (x=1–3) with CH₄ and H₂ have been compared with the previously reported results of Group 8 analogues [OsO_x]⁺/CH₄/H₂ (x=1–3) and the [FeO]⁺/H₂ system. The electronic origins for their distinctly different reaction behaviors have been addressed.     

Use of ethyl oxamate for syntheses of oxamato(-1) and novel μ-oxamato(-2) complexes

Summary The use of ethyl oxamate for the synthesis of inorganic oxamato complexes is reported. A reaction system leading to the preparation of the novel polymeric -oxamato(-2) complexes [M(oxm)(H₂O)₂] _x (M=Cu, Zn, Cd), [Co(oxm)(H₂O)₂] _x ·0.5xH₂O and [Ni(oxm)(H₂O)₂] _x ·xH₂O is described (H₂ oxm = oxamic acid). Ethyl oxamate can also be used for the preparation of monomeric oxamato(-1) complexes.

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Der Einsatz von Ethyloxamat für die Synthese von Oxamato(-1) und neuen -Oxamato(-2)-Komplexen (Kurze Mitt.)

Zusammenfassung Es wird der Einsatz von Ethyloxamat für die Synthese von anorganischen Oxamato-Komplexen beschrieben. Ein Reaktions-System für die Herstellung von neuen -Oxamato(-2)-Komplexpolymeren: [M(oxm)(H₂O)₂] _x ; (M = Cu, Zn, Cd), [Co(oxm)(H₂O)₂] _x ·0.5xH₂O und [Ni(oxm)(H₂O)₂] _x ·xH₂O, wird vorgestellt. Ethyloxamat kann auch für die Herstellung von monomeren Oxamato(-1)-Komplexen verwendet werden.

     

Study of hydroformylation of formaldehyde in the presence of rhodium catalysts byin situ IR spectroscopy and the kinetic technique

Carbonylrhodium complexes formed during hydroformylation of CH₂O from various rhodium precursors were investigated byin situ IR spectroscopy. It was found that under the conditions of the hydroformylation of CH₂O inN,N-dimethylacetamide (DMAA), RhH(CO)(PPh₃)₃, RhCl(CO)(PPh₃)₂, RhCl(PPh₃)₃, RhCl(CO)(PBu₃)₂, and [RhCl(CO)₂]₂ form complex systems that necessarily contain anionic complexes, [Rh(CO)₂L_x(DMAA)_y]^– (L = PPh₃, PBu₃,x = 1 to 2,y = 1 to 0; [Rh(CO)₄]^–). The participation of ionic structures in the hydroformylation of CH₂O, most likely, in the step of the activation of CH₂O, was proven by kinetic techniques.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1066–1069, June, 1995.     

Analyse von Kernresonanzspektren in Einkristallen niedriger Symmetrie II: trans-[Cr en2Cl2] Cl · HCl · xH2O,trans- [Co en2Cl2] Cl · HCl · xH2O

Zusammenfassung In Einkristallen von trans- [Cr en₂ Cl₂] Cl · HCl · xH₂O und trans- [Co en₂ Cl₂] Cl · HCl · xH₂O wurden die Kernquadrupolkopplungstensoren am komplex gebundenen und am ionischen Chlor mit der Methode der konstanten Frequenzen aus der magnetischen Kernresonanz bestimmt. Die Ergebnisse wurden zur Abschätzung des Ionencharakters der Metall-Halogen-bindung verwendet.

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The nuclear quadrupole coupling tensor was determined for all chlorine nuclei in single crystals of trans-[Cr en₂ Cl₂] Cl · HCl · xH₂O and trans- [Co en₂ Cl₂] Cl · HCl · xH₂O from nuclear magnetic resonance data by the method of constant frequencies. The results were used to determine the approximate ionic character of the metal halogen bonds.

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Résumé Appliquant la méthode des fréquences constantes aux résonances magnétiques nucléaires nous avons déterminé les tenseurs de couplage quadripolaire nucléaire du Cl complexé et ionique dans les monocristaux de trans- [Cr en₂ Cl₂] Cl · HCl · xH₂O et trans- [Co en₂ Cl₂] Cl · HCl· xH₂O. A l'aide des résultats le caractère ionique des liaisons métal-chlore est évalué.

     

Tetraalkylammonium fluorooxoperoxovanadates

Summary Compounds crystallizing from theMOH-HF-V₂O₅-H₂O₂-H₂O (M=N(CH₃)₄, N(C₂H₅)₄, N(C₄H₉)₄) system have been characterized by elemental analysis, vibrational spectra, and X-ray powder patterns. Besides [N(CH₃)₄]₂[VO(O₂)₂F]·2H₂O (1) and [N(CH₃)₄]₃[V₂O₂(O₂)₄F] (2) which correspond to the known compoundsM ₂[VO(O₂)₂F] (M=K, NH₄, Cs) and (NH₄)₃[V₂O₂(O₂)₄F]·2H₂O, respectively, complexes of two new types have been obtained: [N(C₂H₅)₄]₂[V₂O_5–x (O₂) _x F₂]·H₂O(x0.25,3) and the first trinuclear peroxo complex of vanadium(V), [N(C₄H₉)₄]₂[V₃O₃(O₂)₄F₃]·6H₂O(4).

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Tetraalkylammonium-Fluorooxoperoxovanadate

Zusammenfassung Aus dem SystemMOH-HF-V₂O₅-H₂O₂-H₂O (M=N(CH₃)₄), N(C₂H₅)₄, N(C₄H₉)₄) kristallisierende Verbindungen wurden mittels Elementaranalyse, Schwingungsspektroskopie und Röntgendiffraktion charakterisiert. Neben [N(CH₃)₄]₂[VO(O₂)₂F]·2H₂O (1) und [N(CH₃)₄]₃][V₂O₂(O₂)₄F] (2), welche den bekannten VerbindungenM ₂[VO(O₂)₂F] (M=K, NH₄, Cs) und (NH₄)₃[V₂O₂(O₂)₄)F]·2H₂O entsprechen, wurden zwei neue Typen von Komplexen erhalten: [N(C₂H₅)₄]₂[V₂O_5–x (O₂) _x F₂]·H₂O (x0.25,3) und der erste dreikernige Peroxokomplex von Vanadium(V), [N(C₄H₉)₄]₂[V₃O₃(O₂)₄F₃]·6H₂O (4).

     

Bacterial activity of cobalt(III) complexes. Part IV: Diethylenetriaminemonoacetatocobalt(III) complexes

Summary The activities of the diethylenetriaminemonoacetatocobalt(III) complexes, [Co(en)(DTMA)]I₂, [CoX₂(DTMA)] and [CoCO₃(DTMA)]·H₂O (DTMA=diethylenetriaminemonoacetato or formally 3-amino-3, 6-diazaoctanato; en=ethylenediamine, X=Cl^–, NO ₂ ^– , NCS^–) were studied onEscherichia coli B growing in a minimal glucose medium in both lag- and log-phases. Activities decrease in the order: [Co(NCS)₂(DTMA)]> [Co(NO₂)₂(DTMA)]>[Co(en)(DTMA)]I₂>[CoCl₂(DTMA)] >[CoCO₃(DTMA)]·H₂O. The antagonistic activities of the complexes were also studied.     

Labelling Studies to Determine Product Formation from Reactions of CO and Hydrogen Catalysed by Ru Clusters and Rh Complexes

Reaction of CO with hydrogen in the presence of [Ru₃(CO)₁₂], KI and N-methylpyrrolidone produces small amounts of methanol under mild conditions. Using D₂ the methanol is CD₃OD confirming that it is a product of CO hydrogenation. In the presence of added H₂O, CH _x D_1-y OH/D (y=0–3) are produced. Carrying out the same reaction in the presence of MeI water and RhCl₃·xH₂O (x=3–4) produces ethanoic acid in a slow reaction which continues for at least 64 h. The effects of different reaction parameters are discussed and labelling using ¹³CH₃I shows that some of the ethanoic acid originates from sources other than MeI whilst labelling with D₂, CD₃I, and/or D₂O suggest that some originates from CO and H₂. Electrospray mass spectrometry and high pressure infra-red spectroscopic studies show that the main species present in catalytic solutions are [HRu₃(CO)₁₁]⁻, [HRu₄(CO)₁₃]⁻ and [Ru(CO)₃I₃]⁻ for methanol carbonylation, [Ru(CO)₃I₃]⁻ and [RhI₂(CO)₂]⁻ for ethanoic acid production. A reaction carried out in the absence of [Ru₃(CO)₁₂] gave similar results to a reaction in which it was added, suggesting that the entire process may be catalysed by rhodium complexes alone. Electronic Supplementary Material  Supplementary material for this article is available at and is accessible for authorized users.

Kinetic studies in mass spectrometry–VII: Competing cleavage and rearrangement processes in molecular ion decomposition reactions

Apparently competing cleavage and rearrangement reactions in a series of molecular ions have been studied by ionization and appearance potential methods, and by determination of the electron energy dependence of both normal and metastable daughter ion peak intensities. The processes investigated were (i) [M ? CH₃] vs. [M ? CH₂O] in anisole; (ii) [M ? OC₆H₅] vs. [M ? CO] in phenyl ether; (iii) [M ? NO₂] vs. [M ? NO] in nitrobenzene; (iv) [M ? C₃H₇] vs. [M ? C₂H₄] in butyrophenone: (v) [M ? C₃H₇] vs. [M ? C₃H₆] in n-butylbenzene; (vi) [M ? CH₂OH] vs. [M ? CH₂O] in 2-phenylethanol; (vii) [M ? CH₃CO₂] vs. [M ? CH₂CO] in benzyl acetate; and (viii) [M ? C₄H₉O] vs. [M ? C₄H₇] in n-butylbenzoate. The results are interpreted in terms of k vs. E curves with very different frequency factors for the two reaction types. Appearance potentials of metastable ions for the rearrangement reactions have also been measured.     

Synthesis, spectral characterization and crystal structure of copper(II) complexes of 2-benzoylpyridine-N(4)-phenylsemicarbazone

An interesting series of nine new copper(II) complexes [Cu₂L₂(OAc)₂]·H₂O (1), [CuLNCS]·½H₂O (2), [CuLNO₃]·½H₂O (3), [Cu(HL)Cl₂]·H₂O (4), [Cu₂(HL)₂(SO₄)₂]·4H₂O (5), [CuLClO₄]·½H₂O (6), [CuLBr]·2H₂O (7), [CuL₂]·H₂O (8) and [CuLN₃]·CH₃OH (9) of 2-benzoylpyridine-N(4)-phenyl semicarbazone (HL) have been synthesized and physico-chemically characterized. The tridentate character of the semicarbazone is inferred from IR spectra. Based on the EPR studies, spin Hamiltonian and bonding parameters have been calculated. The g values, calculated for all the complexes in frozen DMF, indicate the presence of the unpaired electron in the d_x²-y² orbital. The structure of the compound, [Cu₂L₂(OAc)₂] (1a) has been resolved using single crystal X-ray diffraction studies. The crystal structure revealed monoclinic space group P2₁/n. The coordination geometry about the copper(II) in 1a is distorted square pyramidal with one pyridine nitrogen atom, the imino nitrogen, enolate oxygen and acetate oxygen in the basal plane, an acetate oxygen form adjacent moiety occupies the apical position, serving as a bridge to form a centrosymmetric dimeric structure.     

Guest‐, Light‐ and Thermally‐Modulated Spin Crossover in [FeII2] Supramolecular Helicates

A new bis(pyrazolylpyridine) ligand (H₂L) has been prepared to form functional [Fe₂(H₂L)₃]⁴⁺ metallohelicates. Changes to the synthesis yield six derivatives, X@[Fe₂(H₂L)₃]X(PF₆)₂?xCH₃OH ( 1 , x=5.7 and X=Cl; 2 , x=4 and X=Br), X@[Fe₂(H₂L)₃]X(PF₆)₂?yCH₃OH?H₂O ( 1 a , y=3 and X=Cl; 2 a , y=1 and X=Br) and X@[Fe₂(H₂L)₃](I₃)₂?3 Et₂O ( 1 b , X=Cl; 2 b , X=Br). Their structure and functional properties are described in detail by single‐crystal X‐ray diffraction experiments at several temperatures. Helicates 1 a and 2 a are obtained from 1 and 2 , respectively, by a single‐crystal‐to‐single‐crystal mechanism. The three possible magnetic states, [LS–LS], [LS–HS], and [HS–HS] can be accessed over large temperature ranges as a result of the structural nonequivalence of the Fe^II centers. The nature of the guest (Cl^? vs. Br^?) shifts the spin crossover (SCO) temperature by roughly 40 K. Also, metastable [LS–HS] or [HS–HS] states are generated through irradiation. All helicates (X@[Fe₂(H₂L)₃])³⁺ persist in solution.     

Bis(cyclopentadienyl)methan-verbrückte Zweikernkomplexe,V. Heteronukleare Co/Rh-, Co/Ir-, Rh/Ir- und Ti/Ir-Komplexe mit dem Bis(cyclopentadienyl)methan-Dianion als Brückenliganden

Bis(cyclopentadienyl)methane-bridged Dinuclear Complexes, V^[1]. – Heteronuclear Co/Rh-, Co/Ir-, Rh/Ir-, and Ti/Ir Complexes with the Bis(cyclopentadienyl)methane Dianion as Bridging Ligand^* The lithium and sodium salts of the [C₅H₅CH₂C₅H₄]^- anion, 1 and 2 , react with [Co(CO)₄I], [Rh(CO)₂Cl]₂, and [Ir(CO)₃Cl]n to give predominantly the mononuclear complexes [(C₅H₅-CH₂C₅H₄)M(CO)₂] ( 3, 5, 7 ) together with small amounts of the dinuclear compounds [CH₂(C₅H₄)₂][M(CO)₂]₂ ( 4, 6, 8 ). The ¹H- and ¹³C-NMR spectra of 3, 5 , and 7 prove that the CH₂C₅H₅ substituent is linked to the π-bonded ring in two isomeric forms. Metalation of 5 and 7 with nBuLi affords the lithiated derivatives 9 and 10 from which on reaction with [Co(CO)₄I], [Rh(CO)₂Cl]₂, and [C₅H₅TiCl₃] the heteronuclear complexes [CH₂(C₅H₄)₂][M(CO)₂][M′(CO)₂] ( 11–13 ) and [CH₂(C₅H₄)₂]-[Ir(CO)₂][C₅H₅TiCl₂] ( 17 ) are obtained. Photolysis of 11 and 12 leads almost quantitatively to the formation of the CO-bridged compounds [CH₂(C₅H₄)₂][M(CO)(μ-CO)M′(CO)] ( 14, 15 ). According to an X-ray crystal structure analysis the Co/Rh complex 14 is isostructural to [CH₂(C₅H₄)₂][Rh₂(CO)₂(μ-CO)] ( 16 ).     

Double complexes [Co(NH3)5(H2O)]2[Zr3F18]·6H2O and [Co(NH3)6]2[Zr3F18]·6H2O

The structures of orthorhombic bis[pentaammineaquacobalt(III)] tetra‐μ₂‐fluorido‐tetradecafluoridotrizirconium(IV) hexahydrate (space group Ibam), [Co(NH₃)₅(H₂O)]₂[Zr₃F₁₈]·6H₂O, (I), and bis[hexaamminecobalt(III)] tetra‐μ₂‐fluorido‐tetradecafluoridotrizirconium(IV) hexahydrate (space group Pnna), [Co(NH₃)₆]₂[Zr₃F₁₈]·6H₂O, (II), consist of complex [Co(NH₃)_x(H₂O)_y]³⁺ cations with either m [in (I)] or and 2 [in (II)] symmetry, [Zr₃F₁₈]⁶⁻ anionic chains located on sites with 222 [in (I)] or 2 [in (II)] symmetry, and water molecules.     

Synthesis,infrared spectra and thermoanalytical properties of transition metal sulfite hydrazine hydrates

Transition metal sulfite hydrazine hydrates, MSO₃·xN₂H₄·yH₂O whereM=Mn, Fe, Co, Ni and Zn have been prepared and characterized by chemical analysis, infrared spectra, thermoanalytical and combustion studies. The colours,x andy parameters of the complexes varied depending upon the preparation conditions. Thermal decomposition characteristics differ from metal to metal yielding metal oxides at relatively low temperatures.

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Zusammenfassung Mittels chemischer Analyse, IR-Spektren, thermoanalytischen und Verbrennungsstudien wurden die Hydrazinhydrate der hergestellten Übergangsmetallsulfite MSO₃·xN₂H₄·yH₂O mitM=Mn, Fe, Co, Ni und Zn beschrieben. Farbe sowie die Parameterx undy der Komplexe hängen von den Herstellungsbedingungen ab. Die thermische Zersetzung, bei der bei relativ niedrigen Temperaturen Metalloxide entstehen, ist von Metall zu Metall verschieden.

     

The thermal decomposition of some Cr(III) complexes

The thermal decomposition reactions of the following chromium(III) complexes were investigated: Cr(CH₃COO)₃·2 H₂O, [C_r3O(CH₃COO)₆(H₂O)₃]Cl·2 H₂O and [Cr₃O(CH₂ClCOO)₆(H₂O)₃]Cl·6H₂O. Simultaneous TG/DTG/DTA were applied nonisothermal conditions. From the recorded curves, the activation energiesE _a were calculated for all the thermal decomposition steps. Appropriate chemical reactions were attributed to the thermal effects, with consideration to the X-ray diffraction and IR spectra results.

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Zusammenfassung Für die Untersuchung der thermischen Zersetzungsreaktion der Chrom(III)-Komplexe Cr(CH₃COO)₃·2H₂O [C_r3O(CH₃COO)₆·(H₂O)₃]Cl2H₂O und [C_r3O(CH₂ClCOO)₆·(H₂O)₃]C₁₆H₂O wurde simultane TG/DTG/DTA unter nichtisothermen Bedingungen eingesetzt. Ausgehend von den aufgezeichneten Kurven wurden für alle Schritte der Zersetzungsreaktion die E_a-Werte berechnet. In Übereinstimmung mit röntgenographischen und IR-spektroskopischen Ergebnissen wurden den thermischen Effekten passende chemische Reaktionen zugeordnet.

     

Crystal Structure of Monoprotonated Cobalt(II) Nitrilotriacetate Tetrahydrate Co(HNta) · 4H2O

X-ray diffraction analysis of Co(HNta) · 4H₂O (I) (H₃Nta = N(CH₂COOH)₃) revealed that its crystals are isostructural to a Zn analog and built from [Co(HNta)(H₂O)₃] complex molecules and crystallization water. The octahedral coordination of the Co atom includes two O atoms and an N atom provided by the chelating tridentate HNta^2–ligand (average Co–O (Nta) 2.055 Å and Co–N 2.205 Å) and three O atoms of water molecules on the shared face (average Co–O(w) 2.105 Å).     

Cobalt Carbonyls Stabilized by N,P-Ligands: Synthesis,Structure, and Catalytic Property for Ethylene Oxide Hydroalkoxycarbonylation

Reactions of N,P-Ligands as Ph₂P(o-NMe₂C₆H₄) (¹L), 2,6-iPr₂C₆H₃NHC(Ph)=NC₆H₄(o-PPh₂) (²L), and Ph₂PN(R)PPh₂ (R=iPr (³L), cyclo-C₆H₁₁ (⁴L), tBu (⁵L), CH₂C₄H₇O (⁶L)) each with dicobalt octacarbonyl produced complexes [¹LCo(CO)₃]₂ ( 1 ), [²LCo(CO)(μ-CO)₂Co(CO)₃] ( 2 ), [³LCo(CO)₃]⁺[Co(CO)₄]⁻ ( 3 ), [³LCo(CO)₂]₂ ( 4 ), [⁴LCo(CO)₂]₂ ( 5 ), [⁵LCo(CO)₂]⁺[Co(CO)₄]⁻ ( 6 ), and [⁶LCo(CO)₂]⁺[Co(CO)₄]⁻ ( 7 ). Complexes 1–7 have all been structurally characterized by X-ray crystallography, IR and NMR spectroscopies, and elemental analysis. Catalytic tests on transformation of ethylene oxide (EO), CO and MeOH into methyl 3-hydroxypropionate (3-HMP) indicate that complexes 1 – 7 are active, where ion-pair complexes 3 and 6 – 7 behave more excellently (by achieving 88.4–93.6% 3-HMP yields) than the neutral species 1 – 2 and 4 – 5 (35.0–46.5% 3-HMP yields) when the reactions are all operated at 2 MPa CO pressure and 50 °C in MeOH solvent. Density functional theory (DFT) study by selecting 3 as a model suggests a cooperative catalytic reaction mechanism by [Co(CO)₄]⁻ and its counter cation [³LCo(CO)₃]⁺. The cobalt-homonuclear ion-pair catalyzed hydroalkoxycarbonylation of EO is present herein.     

Synthesis and Properties of Acidic 3d-Metal Urates

Acidic urates [Mn(HL)₂] · H₂O, [FeOH(HL)₂]₂ · 4H₂O, [Co(HL)₂(H₂O)₂] · 2H₂O, and [Ni(HL)₂(H₂O)₂] · 2H₂O (H₂L is uric acid) were synthesized and their structures and physicochemical properties were studied using IR spectroscopy, diffuse reflection spectroscopy, DTA, and magnetochemistry methods. The metals were shown to coordinate the urate anion through oxygen and nitrogen atoms. The [FeOH(HL)₂]₂ · 4H₂O complex has a dimeric structure.     

Binuclear cyanide-bridged cobalt–iron complexes

Three new binuclear complexes: [(NO)(CN)₄FeCN–Co(en)₂] · H₂O (1), [(NO)(CN)₄FeCN–Co(pn)₂] · 2H₂O (2), and [(NO)(CN)₄FeCN–Co(tn)₂] · 3H₂O (3) (en = ethylenediamine, pn = 1,2-diaminopropane; tn = 1,3-diaminopropane) have been prepared and their properties studies by i.r., u.v. spectroscopy, cyclic voltammetry, and by magnetic measurements.     

New crystal forms of tris(2-aminoethanolato-O,N)cobalt(III): Structures and properties

Crystal forms of cobalt(III) tris(2-aminoethanolate) hydrates, i.e., red cubic crystals of the composition fac-[Co(NH₂CH₂CH₂O)₃] · 5.44H₂O (fac-I · 5.44H₂O) and blue prismatic crystals of the composition mer-[Co(NH₂CH₂CH₂O)₃] · 3H₂O (mer-I · 3H₂O) were studied by the ⁵⁹Co, ¹³C NMR and X-ray diffraction methods. It was found that mer-[Co(NH₂CH₂CH₂O)₃] · 3H₂O (mer-I · 3H₂O) is a new pseudopolymorphic modification of fac-[Co(NH₂CH₂CH₂O)₃] · 3H₂O (fac-I · 3H₂O), while fac-I · 3H₂O represents a new polymorphic modification of the complex mer-[Co(NH₂CH₂CH₂O)₃] · 3H₂O (mer-I · 3H₂O) described previously. The comparative analysis of the spectra revealed dynamic equilibrium between these geometric isomers; the fac-isomer is stable in aqueous solutions.     

Formation and transformation of Amminecarbonatocobalt(III) Complexes

The preparation is described of [CoCO₃(NH₃)₅]ClO₄ · H₂O, trans-[CoCO₃(NH₃)₄(¹⁵NH₃)]ClO₄, and trans-[CoCO₃(NH₃)₄(NH₂CH₃)]ClO₄. The transformation reactions of these complexes, in which a chelate carbonate ligand is formed and one NH₃ is eliminated, were studied in solution and in the solid state. ¹H NMR spectroscopy is used for the identification of the products. It is shown that the transformation reactions are not stereospecific.